CN106238747A - The preparation method of a kind of multistage copper/nano cuprous oxide wire material and glucose sensor electrode based on this material - Google Patents
The preparation method of a kind of multistage copper/nano cuprous oxide wire material and glucose sensor electrode based on this material Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of multistage copper/nano cuprous oxide wire material and glucose sensor electrode based on this material, the two-step method oxidation processes copper nano-wire combined by dry air and wet air, can be obtained inside and have the over-expense classification copper/Red copper oxide heterogeneous nuclear shell structure nano line of regular heterogeneous interface.This structure with under the coupling of the high cuprous outer layer of selective catalysis active oxidation and nanometer sheet branch, shows catalysis activity, sensitivity, capability of fast response, selectivity and the stability in use of excellence at high conductivity fine copper nano wire kernel in glucose electroxidation is applied.The glass carbon sensor electrode that the preparation method of glucose sensor electrode based on multistage copper/nano cuprous oxide wire material obtains, there is good extended storage stability, corrosion resistance, during detection, it is not easily susceptible to the interference of oxygen and chloride ion, can be used for the highly sensitive quick detection of glucose.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to the system of a kind of multistage copper/nano cuprous oxide wire material
Preparation Method and glucose sensor electrode based on this material.
Background technology
Along with the development of material progress and the change of dietary structure of the mankind, diabetes are the most climing in the whole world
Prolonging, owing to it has certain disguise, often patient perceives the when of discomfort late, the lethal danger of diabetes also because of
This is greatly increased, so people are also referred to as " silent killer ".Thus effectively preventing the premise of onset diabetes is to blood glucose
Concentration detects real-time.Except medical diagnosis, biological treatment, environmental monitoring, food industry etc. are also to glucose content
There is wilderness demand in monitoring, these all promote the correlational study of glucose sensor.Till now, glucose experienced by life
Thing enzyme sensor is to the development of the non-enzyme sensor of noble metal, but due to enzyme intrinsic property and the impact of the easy poisoning and deactivation of noble metal,
The stability of this two classes sensor is the most barely satisfactory.Moreover, high cost and low selectivity all make this two classes sensor greatly
Sizable application is severely limited.Then, research worker will more focus on based on transition metal material warp
Ji is worth higher non-enzyme sensor, and Cu and its oxides is representative therein.
Research finds, copper has a highest susceptiveness, but less stable, and its selectivity mostlys come from the portion on surface
Divide the impact of oxidation；Oxidation state copper product catalytic performance is higher, and selectivity is also improved, but makes owing to conductive capability dies down
Its sensitivity declines.Therefore, if the oxidized derivatives of copper and copper is combined composition composite, it is possible to properly settle this
One problem.
Summary of the invention
The shortcomings such as and response time length poor for current non-enzymatic glucose sensor sensitivity poisoning low, easy, selectivity,
The first object of the present invention there is provided the preparation method of a kind of multistage copper/nano cuprous oxide wire material.
The present invention uses following technical scheme:
A kind of preparation method of multistage copper/nano cuprous oxide wire material, including:
Step 1: sodium hydroxide solution and copper-bath are mixed and stirred for uniformly in conical flask, described sodium hydroxide
Solution concentration is 8 to 9 mol/L, and the concentration of described copper-bath is 0.2 to 0.3 mol/L；
Step 2: the conical flask filling mixed solution described in step 1 is heated one hour in oil bath or water-bath, oil bath or
The liquid level of water-bath did not had the height of mixed solution in conical flask, at the uniform velocity stirred mixed solution in heating process；
Step 3: solution system temperature to be mixed reach 70 degrees Celsius to time in 100 degree Celsius range, inject rapidly second two
Amine and hydrazine hydrate, the ratio of copper sulfate and the amount of ethylenediamine material in the range of 0.08 to 0.10, copper sulfate and hydrazine hydrate material
The ratio of amount, in the range of 0.55 to 0.8, maintains mixed solution temperature, until obtaining the nano wire product of copper red color；
Step 4: step 3 is obtained nano wire product ethanol and water washs three times respectively, the nanometer that washing has been enriched with
Line product carries out heat temperature raising in being placed in the quartz ampoule of tubular heater, is warmed up in the range of 60 degrees Celsius to 70 degrees Celsius,
Then passing to dry air, in dry air atmosphere, nano wire product is dried oxidation, dry air atmosphere humidity is low
In 3%, being dried oxidization time in the range of 50 minutes to 60 minutes, keep in quartz ampoule after being dried oxidation temperature-resistant leads to again
Enter wet air to be aged, wet air atmosphere moisture in the range of 65% to 70%, digestion time at 200 minutes extremely
In the range of 210 minutes, the product after ageing takes out and seals up for safekeeping.
The second object of the present invention there is provided a kind of glucose based on above-mentioned multistage copper/nano cuprous oxide wire material
The preparation method of sensor electrode.
A kind of glucose sensor electrode based on multistage copper/nano cuprous oxide wire material, is prepared by following method,
Including,
Step 1: by the glass-carbon electrodes of a diameter of 3 millimeters respectively with the abrasive paper for metallograph having adsorbed 1 micrometer alumina suspension
With the abrasive paper for metallograph sanding and polishing having adsorbed 0.05 micrometer alumina suspension；
Step 2: the glass-carbon electrode that sanding and polishing in step 1 is good is successively placed in dehydrated alcohol and deionized water ultrasonic clearly
Wash 3 minutes post-dryings；
Step 3: the multistage copper/nano cuprous oxide wire film prepared is placed in the glassy carbon electrode surface after cleaning, then
Drip 5 microlitre perfluorosulfonic acid type polymer solutions and at room temperature to dry on glass-carbon electrode.
The invention have the advantages that:
The preparation method of multistage copper/nano cuprous oxide wire material that the present invention provides, by using Hydrothermal Synthesis with low
Warm air oxidizing process, can produce a large amount of target product at short notice, and productivity is higher than 95%.This preparation method avoids tradition
High Temperature High Pressure harsh conditions in chemical vapor deposition method, just can be carried out under the atmospheric pressure environment less than 100 degrees Celsius.Meanwhile,
The method tail gas in process of production is mainly composed of nitrogen, will not pollute surrounding.Additionally, due to be first dried
In air, the effect of the oxide film protection layer that pretreatment is formed, can keep whole material to have the most regular nano wire kernel
Structure, and the air under moistening atmosphere later and moisture, reduce the potential barrier of copper nano-wire (100) crystal face, to trigger along <
002 > epitaxial growth radially (being perpendicular to nano wire axial) serves facilitation, dramatically increases the specific surface of nano wire product
Long-pending.This nanowire preparation method can effectively control nanowire size and construction, it is possible to prepared by the magnanimity realizing feather weight, and weight
Renaturation is good.Multistage copper/nano cuprous oxide wire structure tool has been widely used, and can be widely applied to clinical medicine, biology, change
The fields such as, chemical industry.
There is inside gained of the present invention the classification copper/Red copper oxide heterogeneous nuclear shell structure nano line of regular heterogeneous interface,
Under the coupling of high conductivity fine copper nano wire kernel and the high cuprous outer layer of selective catalysis active oxidation and nanometer sheet branch,
The application of glucose electroxidation shows the catalysis activity of excellence, sensitivity (1420.7 μ A/mMcm2), capability of fast response
(response time < 0.1s), selectivity and stability in use.Glucose based on multistage copper/nano cuprous oxide wire material passes
The glass carbon sensor electrode that the preparation method of sensor electrode obtains, has good extended storage stability, and corrosion resistance, in inspection
It is not easily susceptible to the interference of oxygen and chloride ion during survey, can be used for the highly sensitive quick detection of glucose, to home-use micro-
The commercialization large-scale production of type sensor has great importance.
Accompanying drawing explanation
Fig. 1 is the XRD spectra relative analysis figure of copper/nano cuprous oxide wire that copper nano-wire obtains with embodiment 1.
Fig. 2 is the high-resolution SEM phenogram of embodiment 1 bronze medal/nano cuprous oxide wire product.
Fig. 3 is the spot scan element energy spectrum analysis figure of embodiment 1 bronze medal/nano cuprous oxide wire product.
Fig. 4 is the TEM phenogram of embodiment 1 bronze medal/nano cuprous oxide wire product.
A is low power TEM photo；B, c, d are respectively the high magnification map in α, β and γ region in a, and e is b, the electronics of c, d figure
Diffraction spectrogram, f is the Fourier transformation in moire fringes region.
Fig. 5 is current time response curve during electrochemical measurement in embodiment 2.
Fig. 6 is response time curve during electrochemical measurement in embodiment 2.
Fig. 7 is glucose content calibration curve figure during electrochemical measurement in embodiment 2.
Fig. 8 is sample antioxygen gas and chloride ion interference test figure in experimental example 1.
Fig. 9 is the sample chrono-amperometric response diagram to disturbance thing in experimental example 2.
Figure 10 is the long-time stability investigation figure of sample in experimental example 3.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is specifically described:
Embodiment 1
A kind of preparation method of multistage copper/nano cuprous oxide wire material, including,
Step 1:80 gram sodium hydroxide is dissolved in 300 ml deionized water, with 10 after sodium hydroxide solution cools down slightly
The copper-bath of milliliter is mixed and stirred for 15 minutes, and the concentration of copper-bath is 0.05 grams per milliliter, and stirring uses magnetic force to stir
Mix or mechanical agitation；
Step 2: the conical flask filling above-mentioned homogeneous mixture solotion heated in 90 degrees Celsius of oil baths, the liquid level of oil bath is wanted
Not having the height of mixed solution in conical flask, uniform stirring solution in heating process, stirring uses magnetic agitation, magnetic in conical flask
Rotor speed is 400 revs/min；
Step 3: when solution system temperature to be mixed reaches 90 degrees Celsius, the syringe using range to be 5 milliliters adds rapidly
Enter 2.5 milliliters of ethylenediamines, then add 0.2 milliliter of hydrazine hydrate with the injection that another range is 1 milliliter, be further continued for heating afterwards
50 minutes, obtain the nano wire product of copper red color；
Step 4: respectively washed three times by the nano wire product second alcohol and water of gained in step 3, washing enrichment process can make
With pumping and filtering device or centrifugation apparatus, the copper nano-wire product that washing has been enriched with is placed in the quartz ampoule of tubular heater, heats up
To 60 degrees Celsius, then pass to dry air, in dry air atmosphere, nano wire product is dried oxidation, dry air
Atmosphere moisture is less than 3%, is dried oxidization time 55, and keep in quartz ampoule after being dried oxidation temperature-resistant is passed through moistening sky again
Gas is aged, and wet air atmosphere moisture is in the range of 65% to 70%, and digestion time is 210 minutes, the product after ageing
Taking-up is sealed up for safekeeping.
Copper nano-wire before Cu NWs refers to oxidation processes in Fig. 1, Cu@Cu2O NS-NWs refers to two-step method oxidation processes
After classification copper/nano cuprous oxide wire.Fig. 1 has investigated nano wire product after original copper nano wire aoxidizes with two-step method
XRD, contrast finds to occur in that Emission in Cubic copper and Red copper oxide in the sample of oxidation processes, respectively with copper standard card simultaneously
(JCPDS, 85-1326) and Red copper oxide standard card (JCPDS, 05-0667) are consistent.
Fig. 2 SEM characterization result shows that typical copper/Red copper oxide sample maintains good nano wire trunk structure, directly
In footpath is 90 nanometers to 130 nanometer range, average length is more than 5 microns, simultaneously it is clear that the surface cloth of nano wire
Expire two grades of nanometer sheet structures, there is wider bottom surface (15 nanometers are to 20 nanometers) and sharp-pointed end form.
Fig. 3 element energy spectrum analysis display oxygen element gradually subtracts to nano wire its energy spectrum signal of trunk nucleus from nanometer sheet
Weak, contrary, copper signal the most gradually strengthens, and illustrates that this nanostructured nucleus degree of oxidation is more weak, and near top layer
Higher with the region Lattice Oxygen content of nanometer sheet.By the nanometer sheet to this structure, nano wire top layer and nano wire axis position
Point by point scanning, finds that the ratio of nanometer sheet and the oxygen atomicity of surface region and copper atom number is about 1:2, and near axis adnexa
Copper content close to 100%.
It is branch-like nano thread structure that Fig. 4 TEM characterizes sample after show further oxidation, the high power of single nano-wire
TEM observation illustrates the nano wire change from axis radially contrast: closer to nanowire surface with extend to surrounding space
Nanometer sheet stub area, contrast is the lowest.The nano wire outer layer of high power TEM display contiguous zone and the obvious heterogeneous boundary of internal layer,
And the spacing of lattice of both sides, demarcation line exists the most different, outside is that interlamellar spacing is relatively big (0.301 nanometer)Inner side is then interlamellar spacing smaller (0.258 nanometer)Nano wire top layer copper atom is described
Stacking is constantly clamp-oned the lattice distance expansion caused due to oxygen atom.From SEAD spectrogram, it can be observed that bright
The diffraction spot that dark two sets are overlapped, a set of FCC single crystal Cu that belongs to, another set of, belong to monocrystalline Red copper oxide, this result
Match with XRD.Meanwhile, from nanometer sheet to nano wire, the Fourier transformation dot pattern of three zoness of different is identical, this
Fully show the formation of this multilevel branch nanometer sheet-nano wire hetero structure be nano wire outer layer in oxidizing process along with copper oxygen
The epitaxially grown result of mutually migration of element.Additionally, the nano wire sample trunk direction of growth after Yang Hua and fine copper nano wire
Unanimously, it is allDirection.Carry out Fourier's image reversal shift by the interface zone that moire fringes is occurred to observe,
Most of lattice fringes can with continuously smooth through heterogeneous interface layer, edgeCu on extension direction2Produced between O and Cu
Raw deformation probability is less than 5%.
Embodiment 2
A kind of glucose sensor electrode based on multistage copper/nano cuprous oxide wire material, is prepared by following method,
Including,
Step 1: by the glass-carbon electrodes of a diameter of 3 millimeters respectively with the abrasive paper for metallograph having adsorbed 1 micrometer alumina suspension
With the abrasive paper for metallograph sanding and polishing having adsorbed 0.05 micrometer alumina suspension；
Step 2: the glass-carbon electrode that sanding and polishing in step 1 is good is successively placed in dehydrated alcohol and deionized water ultrasonic clearly
Wash 3 minutes post-dryings；
Step 3: the multistage copper/nano cuprous oxide wire film prepared is placed in the glassy carbon electrode surface after cleaning, then
Drip 5 microlitres perfluorosulfonic acid type polymer solution (0.34wt%) and at room temperature to dry on glass-carbon electrode.
Glucose sensor electrode is carried out electrochemical measurement: the test of glucose sensor electrode uses three-electrode system
(as to electrode, Ag/AgCl (3M KCl) is reference electrode to platinum filament, and the sodium hydroxide ultra-pure water solution of 5 milliliters of suitable concns is made
For electrolyte) and CHI660D electrochemical workstation complete.The chronoamperometry optimal potential setting of measurement, at 0.6V, drips tested
Solution system is kept to be in stirring Convection states during surveying thing.All of experiment all completes under room temperature (25 DEG C).To classification
Copper/nano cuprous oxide wire load capacity is the Nafion/Cu@Cu of 10 grams2O NS-NWs/GCE modified electrode is from 10 μMs to 0.5M
Concentration of glucose electrolyte solution drips continuously, each concentration in triplicate, wherein 0.5M concentration dripped 8 times highly concentrated to obtain
Current density signal under degree concentration of glucose.
Fig. 5 shows that ampere signal of telecommunication platform constantly carries along with the accumulation of glucose content in dropping concentration and test system
Rising, dropping response time is less than 0.1s (Fig. 6) every time, has shown efficient glucose electro-oxidizing-catalyzing ability.
Fig. 7 further illustrates Nafion/Cu@Cu2O NS-NWs/GCE linear response range is in 0.7 μM to 2.0mM
(R2=0.978), in, sensitivity is 1420.77 μ A/mMcm2, lowest detectable limit to 40nM (S/N=3).
Experimental example 1
In order to assess electrolyte solution environment Nafion/Cu@Cu2The anti-interference of O NS-NWs/GCE, expands it and is giving birth to
Application in reason liquid, especially blood of human body sample, has investigated the impact on modified electrode of oxygen and chloride ion.Keep room temperature
Under the conditions of (25 degrees Celsius), saturated to the saturation of the air, nitrogen respectively and containing 0.1M sodium chloride alkaline electrolyte solution (50mM
Sodium hydroxide solution) in continuously dropping concentration be the GES of 50mM, under 0.6V current potential, measure current time
Curve.
Fig. 8 shows under same experimental conditions, the chrono-amperometric response of regular situation (saturation of the air), satisfies with using nitrogen
With dispel the solution system of dissolved oxygen and the brightest containing the conventional soln system chrono-amperometric response curve of 0.1M sodium chloride
Aobvious difference, this shows to detect the dissolved oxygen in environment and chloride ion all without to Nafion/Cu@Cu2O NS-NWs/GCE examines
Survey glucose performance and bring appreciable impact.The result shows that classification core-shell nano line structure successfully overcomes enzyme glucose
The difficulty that sensor is easily restricted by oxygen factor, it also avoid noble metal non-enzymatic glucose sensor due to the existence of chloride ion
The problem of poisoning and deactivation.
Experimental example 2
The anti-interference test of glucose sensor.Use electrochemical workstation, respectively test 0.1mM polysaccharide (fructose and
Sucrose) and endogenous reductase compound (uric acid, ascorbic acid and acetaminophen) and 1mM glucose solution current-responsive believe
Number.In human body environment, blood sugar concentration generally exceeds 30 times to 50 times than the concentration of polysaccharide and endogenous reductase compound, this reality
Executing the interfering material concentration added in example is 1:10 with concentration of glucose ratio, and this ratio is significantly larger than blood of human body ring
Border.
Fig. 9 shows under the interference of high intensity, Nafion/Cu@Cu2O NS-NWs/GCE electrode still shows Portugal
The specificity of grape sugar.
Experimental example 3
The long-time stability of glucose sensor and repeatability test.To storing one week at normal environmental conditions
Nafion/Cu@Cu2O NS-NWs/GCE electrode, enters under 50mM sodium hydroxide electrolyte solution system and+0.6V operating potential
(every day measures once) is investigated in the response of row chrono-amperometric.
Figure 10 testing result shows, after one week, substantially decaying does not occurs in the sensitivity of this electrode, only 5.45%
Decline.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, and this technology is led
Change that the technical staff in territory is made in the essential scope of the present invention, retrofit, add or replace, also should belong to the present invention's
Protection domain.
Claims (2)
1. the preparation method of multistage copper/nano cuprous oxide wire material, it is characterised in that including:
Step 1: sodium hydroxide solution and copper-bath are mixed and stirred for uniformly in conical flask, described sodium hydroxide solution
Concentration is 8 to 9 mol/L, and the concentration of described copper-bath is 0.2 to 0.3 mol/L；
Step 2: the conical flask filling mixed solution described in step 1 is heated one hour in oil bath or water-bath, oil bath or water-bath
Liquid level do not had the height of mixed solution in conical flask, heating process at the uniform velocity stirs mixed solution；
Step 3: solution system temperature to be mixed reach 70 degrees Celsius to time in 100 degree Celsius range, inject rapidly ethylenediamine with
Hydrazine hydrate, the ratio of copper sulfate and the amount of ethylenediamine material in the range of 0.08 to 0.10, the amount of copper sulfate and hydrazine hydrate material it
Ratio, in the range of 0.55 to 0.8, maintains mixed solution temperature, until obtaining the nano wire product of copper red color；
Step 4: step 3 obtains nano wire product ethanol and water washs three times respectively, nano wire washing being enriched with produces
Product carry out heat temperature raising in being placed in the quartz ampoule of tubular heater, are warmed up in the range of 60 degrees Celsius to 70 degrees Celsius, then
Being passed through dry air, nano wire product is dried in dry air atmosphere oxidation, dry air atmosphere humidity is less than
3%, it is dried oxidization time in the range of 50 minutes to 60 minutes, keep in quartz ampoule after being dried oxidation temperature-resistant is passed through again
Wet air is aged, wet air atmosphere moisture in the range of 65% to 70%, digestion time at 200 minutes to 210
In the range of minute, the product after ageing takes out and seals up for safekeeping.
2. a glucose sensor electrode based on multistage copper/nano cuprous oxide wire material, it is characterised in that by following
Method prepares, including,
Step 1: by the glass-carbon electrodes of a diameter of 3 millimeters respectively with abrasive paper for metallograph and the suction having adsorbed 1 micrometer alumina suspension
The attached abrasive paper for metallograph sanding and polishing of 0.05 micrometer alumina suspension；
Step 2: the glass-carbon electrode that sanding and polishing in step 1 is good is successively placed on ultrasonic cleaning 3 in dehydrated alcohol and deionized water
Minute post-drying；
Step 3: the multistage copper/nano cuprous oxide wire film prepared is placed in the glassy carbon electrode surface after cleaning, then drips 5
Microlitre perfluorosulfonic acid type polymer solution and at room temperature dries on glass-carbon electrode.
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